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X-ray pleochroism is observed near the Se K absorption edge in a monoclinic crystal of selenolanthionine monohydrate using linearly polarized synchrotron radiation and is explained by a simple molecular-orbital model. The complex anomalous-scattering tensor of selenium, measured by diffraction in a tetragonal crystal of the anhydrous compound, exhibits anisotropy nearly 6 for f' and 7 for f”, the most yet found for a K edge. The crystal structure was determined for D-(-)-selenolanthionine, space group P43212, a = 6.651 (2), c =21.758 (5) Å, Z = 4, R = 0.027 for 304 unique reflections.